EP0056449A2 - Molding blends of polyethylene terephthalate - Google Patents

Molding blends of polyethylene terephthalate Download PDF

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Publication number
EP0056449A2
EP0056449A2 EP81109222A EP81109222A EP0056449A2 EP 0056449 A2 EP0056449 A2 EP 0056449A2 EP 81109222 A EP81109222 A EP 81109222A EP 81109222 A EP81109222 A EP 81109222A EP 0056449 A2 EP0056449 A2 EP 0056449A2
Authority
EP
European Patent Office
Prior art keywords
weight
blend
terpolymer
polyethylene terephthalate
blends
Prior art date
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Granted
Application number
EP81109222A
Other languages
German (de)
French (fr)
Other versions
EP0056449A3 (en
EP0056449B1 (en
Inventor
George Joseph Ostapchenko
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Publication of EP0056449A3 publication Critical patent/EP0056449A3/en
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Publication of EP0056449B1 publication Critical patent/EP0056449B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • This invention relates to polyethylene terephthalate molding resins and more particularly to such resins that have good resistance to high velocity impact.
  • Plastic structures have recently gained importance in automotive uses. The strengthening of plastic materials in order to withstand automotive impact forces is continually sought by research personnel. Polyethylene terephthalate has potential in molded plastic automotive parts, but its brittleness on impact can be improved.
  • the susceptibility of polyethylene terephthalate to crack in a brittle fashion on impact is lessened by adding to the polyethylene terephthalate of two additives; namely, an ionomeric terpolymer which is the zinc salt of a terpolymer of ethylene, methacrylic acid, and isobutyl acrylate; and a second terpolymer of ethylene, propylene, and 1,4-hexadiene which has succinate groups pendant from the copolymer chain.
  • the molding blend of this invention consists essentially of
  • the polyethylene terephthalate resin employed herein is well known in the art, and has an inherent viscosity of at least 0.4 deciliters/g, and preferably 0.5-3.0 deciliters/g. It is film and fiber forming. Inherent viscosity (IV) is measured as described in U.S. Patent 4,172,859.
  • the ionomeric terpolymer can be prepared as described in U.S. Patent 3,264,272.
  • the second terpolymer can be prepared by grafting maleic or fumaric acid groups to the terpolymer, as described in U.S. Patent 4,010,223, to obtain succinic groups, namely, a mixture of succinic anhydride and succinic acid, grafted to the terpolymer.
  • the average particle size of the particles of terpolymers b) and c) individually or together (i.e., in agglomerated form) in the blends of this invention should be below 3 microns in order to achieve good resistance to high velocity impact, and preferably the average is between 0.1-3 microns.
  • the terpolymers may agglomerate with themselves or with each other and, in such event, the average agglomerate particle size should be below 3 microns.
  • the blends can be prepared by dry blending, such as tumbling together. The blend is then either extruded into cubes or directly extruded into molded form, such as sheet. Alternatively, the ingredients can be melt blended by melting one or two of the ingredients, then adding the remaining ingredients.
  • compositions of the invention may be modified by incorporation of conventional additives such as fillers (e.g., mica) or reinforcing agents (e.g., glass fibers) up to 40% by weight; thermal, UV, and oxidative stabilizers, dyes, lubricants, pigments, flame retardants and the like.
  • conventional additives such as fillers (e.g., mica) or reinforcing agents (e.g., glass fibers) up to 40% by weight; thermal, UV, and oxidative stabilizers, dyes, lubricants, pigments, flame retardants and the like.
  • a blend of the materials described in the table were prepared by mixing and tumbling in a polyethylene bag.
  • compositions of this invention may be compression molded or thermoformed into parts useful in exterior automotive applications such as body panels and the like.

Abstract

A molding blend of polyethylene terephthalate, a selected ionomeric terpolymer and a selected graft terpolymer provides molded articles of good toughness.

Description

    FIELD OF THE INVENTION
  • This invention relates to polyethylene terephthalate molding resins and more particularly to such resins that have good resistance to high velocity impact.
    • BACKGROUND OF THE INVENTION
  • Plastic structures have recently gained importance in automotive uses. The strengthening of plastic materials in order to withstand automotive impact forces is continually sought by research personnel. Polyethylene terephthalate has potential in molded plastic automotive parts, but its brittleness on impact can be improved.
    • SUMMARY OF THE INVENTION
  • In this invention the susceptibility of polyethylene terephthalate to crack in a brittle fashion on impact is lessened by adding to the polyethylene terephthalate of two additives; namely, an ionomeric terpolymer which is the zinc salt of a terpolymer of ethylene, methacrylic acid, and isobutyl acrylate; and a second terpolymer of ethylene, propylene, and 1,4-hexadiene which has succinate groups pendant from the copolymer chain.
  • Specifically the molding blend of this invention consists essentially of
    • a) polyethylene terephthalate,
    • b) 2 to 20% by weight of blend of an ionomeric terpolymer consisting of 60 to 99% by weight ethylene, 0.5 to 20% by weight methacrylic acid, and 0.5 to 20% by weight isobutyl acrylate, in which the acid moieties are neutralized to the extent of 5 to 100% with divalent metallic cations, preferably zinc ions,
    • c) 2 to 20% by weight of blend of a second terpolymer of 60 to 90% by weight of ethylene, 10 to 38% propylene, 2 to 10% by weight 1,4-hexadiene and 0 to 5% by weight 2,5-norbornadiene which has 0.2 to 9% by weight succinic groups appended to the terpolymer chain.
    DESCRIPTION OF THE INVENTION
  • The polyethylene terephthalate resin employed herein is well known in the art, and has an inherent viscosity of at least 0.4 deciliters/g, and preferably 0.5-3.0 deciliters/g. It is film and fiber forming. Inherent viscosity (IV) is measured as described in U.S. Patent 4,172,859.
  • The ionomeric terpolymer can be prepared as described in U.S. Patent 3,264,272. The second terpolymer can be prepared by grafting maleic or fumaric acid groups to the terpolymer, as described in U.S. Patent 4,010,223, to obtain succinic groups, namely, a mixture of succinic anhydride and succinic acid, grafted to the terpolymer. The average particle size of the particles of terpolymers b) and c) individually or together (i.e., in agglomerated form) in the blends of this invention should be below 3 microns in order to achieve good resistance to high velocity impact, and preferably the average is between 0.1-3 microns. The terpolymers may agglomerate with themselves or with each other and, in such event, the average agglomerate particle size should be below 3 microns.
  • The blends can be prepared by dry blending, such as tumbling together. The blend is then either extruded into cubes or directly extruded into molded form, such as sheet. Alternatively, the ingredients can be melt blended by melting one or two of the ingredients, then adding the remaining ingredients.
  • The compositions of the invention may be modified by incorporation of conventional additives such as fillers (e.g., mica) or reinforcing agents (e.g., glass fibers) up to 40% by weight; thermal, UV, and oxidative stabilizers, dyes, lubricants, pigments, flame retardants and the like.
    • EXAMPLE
  • A. A blend of the materials described in the table were prepared by mixing and tumbling in a polyethylene bag.
  • B. 60 mil thick sheeting was prepared by extruding the blend prepared in Part A using a 28 mm Werner-Pfleiderer twin screw extruder at 280°C and a three-roll finisher for quenching. The sheeting was then heated to 150°C for 1 minute to crystallize the polyethylene terephthalate. The crystallized sheeting samples were then tested at room temperature using a Rheometrics Impact Tester using impact velocities of 30, 3,000 and 30,000 inches per minute (ipm). The results are summarized in Table I.
    Figure imgb0001
  • The 30,000 ipm is about 30 miles per hour velocity. Thus the compositions of this invention may be compression molded or thermoformed into parts useful in exterior automotive applications such as body panels and the like.

Claims (8)

1. A molding blend consisting essentially of
a) polyethylene terephthalate,
b) 2 to 20% by weight of blend of an ionomeric terpolymer consisting of 60 to 99% by weight ethylene, 0.5 to 20% by weight methacrylic acid, and 0.5 to 20% by weight isobutyl acrylate, in which the acid moieties are neutralized to the extent of 5 to 100% with divalent metallic cations,
c) 2 to 20% by weight of blend of a second terpolymer of 60 to 90% by weight ethylene, 10 to 38% by weight propylene, 2 to 10% by weight 1,4-hexadiene and 0 to 5% by weight 2,5-norbornadiene which has 0.2 to 9% by weight succinic groups appended to the terpolymer chain.
2. The molding blend of claim 1 wherein the ionomeric terpolymer and the second terpolymer individually or together have a particle size less than 3.0 micron.
3. Articles molded from the blends of claim 1 or 2.
4. Articles extruded from the blends of claim 1 or 2.
5. An article of claim 4 wherein the article is a sheet.
6. The blend of claim 1 or 2 which additionally contains 1-40% by weight of blend of a filler.
7. The blend of claim 6 wherein the filler is mica.
8. The blend of claim 1 or 2 wherein the divalent metallic cation is zinc.
EP81109222A 1981-01-07 1981-10-29 Molding blends of polyethylene terephthalate Expired EP0056449B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/223,212 US4303573A (en) 1981-01-07 1981-01-07 Molding blends comprising polyester, ionomer resin and grafted EPDM
US223212 1981-01-07

Publications (3)

Publication Number Publication Date
EP0056449A2 true EP0056449A2 (en) 1982-07-28
EP0056449A3 EP0056449A3 (en) 1982-08-11
EP0056449B1 EP0056449B1 (en) 1986-02-12

Family

ID=22835545

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81109222A Expired EP0056449B1 (en) 1981-01-07 1981-10-29 Molding blends of polyethylene terephthalate

Country Status (7)

Country Link
US (1) US4303573A (en)
EP (1) EP0056449B1 (en)
JP (1) JPS57117559A (en)
AU (1) AU543843B2 (en)
BR (1) BR8107175A (en)
CA (1) CA1159183A (en)
DE (1) DE3173776D1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0203739A1 (en) * 1985-05-20 1986-12-03 Imperial Chemical Industries Plc Polymeric film
EP0653461A2 (en) * 1993-11-11 1995-05-17 Kirin Beer Kabushiki Kaisha Container composed of a saturated polyester resin composition
DE10311828A1 (en) * 2003-03-14 2004-09-23 Helmar Haas Device for renovating house connection lines from a ground line

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3110906A1 (en) * 1981-03-20 1982-10-14 Akzo Gmbh, 5600 Wuppertal HYDROPHILE POLYESTER MATERIAL
US4420580A (en) * 1982-02-08 1983-12-13 The Dow Chemical Company Method for preparing filled polyolefin resins and the resin made therefrom
US4397986A (en) * 1982-03-03 1983-08-09 Ethyl Corporation Thermoplastic polyester blends
JPS6270443A (en) * 1985-09-24 1987-03-31 Idemitsu Petrochem Co Ltd Glass fiber-reincorced polyester resin composition
US5021113A (en) * 1987-12-30 1991-06-04 Shell Oil Company Tie layer composition and laminated structures containing same
EP0545973A4 (en) * 1990-08-27 1993-09-15 E.I. Du Pont De Nemours And Company Toughened thermoplastic polyester compositions
US6277905B1 (en) 1999-09-23 2001-08-21 Eastman Chemical Company Process for improving the toughness of PCT formulations by adding rubber impact modifiers
US6951674B1 (en) 2000-11-10 2005-10-04 Scimed Life Systems, Inc. Blended polyurethane interventional balloon
WO2002061013A1 (en) * 2001-02-01 2002-08-08 E.I. Dupont De Nemours And Company Composition suitable for seals and seals made therefrom
JP4171867B2 (en) * 2001-05-25 2008-10-29 東洋製罐株式会社 Method for extruding polymer blend resin
US7326753B2 (en) 2005-02-08 2008-02-05 Momentive Performance Materials Inc. Process for the production of crosslinked polymer employing low VOC-producing silane crosslinker and resulting crosslinked polymer

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4172859A (en) * 1975-05-23 1979-10-30 E. I. Du Pont De Nemours And Company Tough thermoplastic polyester compositions
US4219628A (en) * 1979-04-02 1980-08-26 Eastman Kodak Company Molding composition from polyester blends

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4172859A (en) * 1975-05-23 1979-10-30 E. I. Du Pont De Nemours And Company Tough thermoplastic polyester compositions
US4219628A (en) * 1979-04-02 1980-08-26 Eastman Kodak Company Molding composition from polyester blends

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0203739A1 (en) * 1985-05-20 1986-12-03 Imperial Chemical Industries Plc Polymeric film
US4771108A (en) * 1985-05-20 1988-09-13 Imperial Chemical Industries Plc Polymeric film
EP0653461A2 (en) * 1993-11-11 1995-05-17 Kirin Beer Kabushiki Kaisha Container composed of a saturated polyester resin composition
EP0653461A3 (en) * 1993-11-11 1996-10-09 Kirin Brewery Container composed of a saturated polyester resin composition.
US5714220A (en) * 1993-11-11 1998-02-03 Mitsui Petrochemical Industries, Ltd. Container composed of a saturated polyester resin composition
DE10311828A1 (en) * 2003-03-14 2004-09-23 Helmar Haas Device for renovating house connection lines from a ground line

Also Published As

Publication number Publication date
AU543843B2 (en) 1985-05-02
AU7677281A (en) 1982-07-15
DE3173776D1 (en) 1986-03-27
JPS57117559A (en) 1982-07-22
CA1159183A (en) 1983-12-20
EP0056449A3 (en) 1982-08-11
JPS6339021B2 (en) 1988-08-03
US4303573A (en) 1981-12-01
EP0056449B1 (en) 1986-02-12
BR8107175A (en) 1982-07-20

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